Dye fixing product and process and treating of textiles therewith



Patented Nov. 27, 1951 DYE FIXING PRODUCT AND PROCESS AND TREATING OF TEXTELES THEREWITH Myrtle doanne Spangler, Danville, Va., assignor to Dan River Mills, Incorporated, a corporation of Virginia No Drawing. Application April 3, 1950, Serial No. 153,759

12 class. (01. 8--74) 1 My invention relates to improving the fastness of dyeings on cellulosic textiles and morepanticularly to an improved product and process of manufacture thereof, and the application of this improved product to previously dyed textiles. This application is a continuation-iri part of my application Serial No. 92,960, filed May 12, 1949, andincludes modifications and additionsto the product and processes disclosed in that applica- .tion. ,In this earlier application there is disclosed asan improved dyefixing product a water-soluble, dicyandiamide copper chloride methylol that contains copper in the molecule and is capable of fixing substantive dyes on textiles. The process oimanufacture of that product comprisesreaotin'g dicyandiamide With copper chloride to produce a complex which results from the exothermic reaction, and then reacting this complex with formaldehydein an acid medium, which involves another exothermic reaction and the. final production of thedicyandiamide-copper chloridemethylol condensation product.

One of the characteristic features of this new product is its .fsubstantivity to cellulosic fibers, that is, the irreversible transfer .ofthecondensationproduct from aqueous solution onto the textile material. This characteristic enables prep aration of dilute aqueous solutions of the product and the application of these solutions to textiles by simple steeping or immersion of .the.p1eviously dyed textilematerial in the dilute aqueous solution, followed byriris'inganddrying of the material. This offers definite advantages-over the fpadding. procedures that are required for the related prior art products. Also these prior art products require a curing or heating of the product on the goods and are therefore apt to tender the goods. 7 i M In accordance with invention I may prepare the dyefi'xing' product in different ways, but-in each case the final product is substantive to Gena losic fibers and is applicable to textiles by a simple steeping process. A common feature that characterizes the several variations of the process of manufacture of this productis the initial reaction of the dicyandiamide with an acid material. This reaction hydrolyzes or converts the dicyandiamide into a form that will combine with the copper salt and thereby produce a copper complex, orother wise firmly attach the copper molecule to the dicyandiamide so that neither constituent will wash out of the treated textile material,

on v.

The copper complex or vreactio prod i l li dicyandiamide may be produced by; reacting the dicyandiamide with copper chloride, and this indroly sis reaction product may be reacted with the formaldehyde and then reacted With the copper salt.

The above mentioned alternate procedures for carrying out the process and producing the desired product of this invention are illustrated more particularly by the following:

(a) When the dicyandiamide is reacted first with the copper chloride, in the ratio of one mol of dicyandiamide to 0.22 mol of coppenchlor-ide, an exothermic reaction takes place which produces the intermediate hydrolyzed product, and when this intermediate product is condensed with 1.5 molsoi formaldehyde and 0.75 mol 0t hydro:- chloric acid, the optimum type of condensation product is produced. i

(b) If the dicyandiamide is reacted first with hydrochloric acid in the ratio of one mol of di cyandiamide to 0.44. mol of hydrochloric acid, ,a similar exothermic reaction takes placetothat describedjust above, producing ahydrolyzed intermediate product. (0.44 mol of hydrochloric acid isequivalent to 0.22 mol of copper chloride.) To this product can then be added the 0.22 mol of copper chloride and the remaining 031; mol of hydrochloric acid and the resulting product condensed with 1.5 mols formaldehyde to produce a condensation product similar to that in paragraph (a) above.

(c) The dicyandiamide may be reacted first with hydrochloric acid, as above, in the ratio .of one mol of dicyandiamide to 0.44 mol of hydrochloric acid, and the hydrolyzed intermediate product thus producedmay then be reacted with 1.5 molsqformaldehyde and, the remaining 0.31 mol of hydrochloric acid. After this reaction has talgen place, the 0.22 mol of copper chloride can then be added, and a final condensation product similar. to those produced in paragraphs (a) and (b) above isobtained.

.The essential characteristics 6r that than procedures is that the dicyandiamide be reacted first with an acid oracid salt so as to hydrolyze or convert the dicyandiamide into a form that will combine readily and permanently with the copper. compound. and with formaldehyde. Th desired e ul s; e, se ,9??3i113d. i th d c and mideis reacted in neutral or alkaline medium with the salt.

formaldehyde and then reacted with the copper In that case the end product does not possess a substantivity to cellulosic fibers and must be padded onto the fabric with the disadvantages attendant that procedure.

The efiective hydrolysis of the dicyandiamide being dependent upon the amount of acid or acid salt used, it is important to maintain the proper mol ratio between these constituents. For optimum results these should be used approximately 0.22 mol of copper chloride, or its equivalent, 0.44 mol of hydrochloric acid, to each mold of dicyandiamide. With somewhat less desirable results, this ratio may be varied from approximately 0.15 to 0.30 mol of copper chloride, or 0.30 to 0.60 mol of hydrochloric acid for each mol of dicyandiamide. When less than 0.22 mol of copper chloride or 0.44 mol of hydrochloric acid per mol of dicyandiamide is used, a final condensation product is obtained having properties intermediate between the prior art resins and the above-discussed condensation product in that it does not have the degree of substantivity to cellulosic fibers of the above-discussed condensation product. If more than 0.22 mol of copper chloride is used, the excess can be precipitated from the final resinous product with hydrogen sulfide.

When copper chloride, or other suitable copper salt, is used as the first reactant with the dicyandiamide, it is necessary to add hydrochloric acid or the equivalent to the formaldehyde, which is later condensed with the dicyandiamide-cope per chloride complex. The mol ratio ranges from approximately 0.50 to 1.50 mols of hydrochloric acid t each mol of dicyandiamide, with an optimum of approximately 0.75 mol of hydrochloric acid per mol of dicyandiamide. Similarly, the mol ratio of the formaldehyde, which is reacted with the dicyandiamide-copper chloride may vary from approximately 1.3 to 1.8 mols of formaldehyde per mol of dicyandiamide, with an optimum of approximately 1.5 mols of formaldehyde per mol of dicyandiamide.

Regarding the copper salts or the equivalent acids that-may be used to hydrolyze the dicyandiamide, only certain specific ones will work satisfactorily; namely copper chloride, copper nitrate, hydrochloric acid, and nitric acid. The importance of this selection of salts or acids is indicated by the fact that copper sulfate, or sulfuric acid gives a hydrophobic resinous product, and organic acids or copper salts of organic acids do not cause the reaction to take place.

Illustrative but non-limiting examples of the process of producing the condensation product of my invention are as follows:

Example I 7 5 lbs. of water containing 44.5 lbs. of dicyandiamide are heated to 170 F. by open steam. 20 lbs. of CuClz.2HzO are then added and'the complex forms in 7 to 10 minutes with evolution of heat which raises the temperature to 196-202 F. When this has cooled to 140 F., 50 lbs. of 18 Baum hydrochloric acid are added, immediately followed by '70 lbs. of formaldehyde solution (37%). temperature of the solution is raised to 196-202 F., and the final condensation product is formed.

Example II "75 lbs. of water containing 44.5 lbs. of dicyandiamide are heated to 170 F'., by open steam. 30 lbs. of 18 Baum I-ICl acidare added and the complex form in 7 to 10 minutes with the evolution of heat which raises the temperature of the solution to 196-202 F. 20 lbs. of C1Cl2.2H2O are then added, and the temperature allowed to fall to 140 F. 20 lbs. additional of 18" Baume' hydrochloric acid are then added, immediately followed by '70 lbs. of formaldehyde solution (37 Again by an exothermic reaction the temperature of the solution is raised to 196-202 FL, and the final condensation product is formed.

Example III '75 lbs. of water containing 44.5 lbs. of dicyandiamide are heated to 170 F. by open steam. lbs. of 18 Baum hydrochloric acid are then added and the complex forms in '7 to 10 minutes with the evolution of heat which raises the temperature of the solution to 196-202 F. When this has cooled to 140 F., 20 lbs. additional of 180 Baum hydrochloric acid are added, immediately followed by 70 lbs. of formaldehyde solution (37%). Again by an exothermic reaction the temperature of the solution is raised to 196-202 F. 20 lbs. of CuClaZl-IzO are then added and the final condensation product is formed.

The final condensation product produced by any one of the foregoing procedures may bediluted to the desired extent and the resulting aqueous solution applied to previously dyed textiles for-fixing the dye thereon; that is, to make it more resistant to washing and frequently to light than it would be without this treatment. The applied condensation product renders direct dyes much faster to hot water, soap, and frequently to light, and the product is much easier of application to the textile material than are the prior art products. In the padding procedure required for the priorart products, the products are applied in concentrated form and after removal, by squeeze rolls, of the excess from the treated material, it is dried. Drying of the product on the textile material frequently causes loss in tensile strength.

The improved product of the present invention is easily appliedby steeping; that is, by simply soaking the previously dyed cloth in a suitable vessel containing a water solutionof the condensation product, after which the cloth is rinsed, thus removing the excess acid material, and then dried. In this manner, the cloth is not tendered,

'that is, there is no appreciable loss in tensile Again by an exothermic reaction the V strength, and theapplication of the condensation product to the cloth is simple. and requires less equipment than with the usual padding op: eration.

The amounts of condensation product to be used for fixing the direct dyes on the cloth will vary with the different shades. For example, light shades require approximately 1% by weight of the dyefixing concentrate based on the weight of the cloth; medium shades about 4% and dark shades about 12%. In all cases. sufficient water is added to bring the total weight of the solution to about 12 times the weight of the cloth. Typical examples of application of the dyefixingproduct to dyed textiles are as follows: 7

Example IV lbs. of a light dyed textile 1.0 lb. of the condensation product 1199 lbs. of water Example V 100 lbs. of a medium dyed textile 4.0 lbs. of the condensation product 1196 lbs. of water amass-1 Example 1 V1.

The amount of water is not critical. In allthe above examples 150 gallons of water could be, used.

When the above, aqueous solutions of the condensation product are applied to the dyed goods by steeping, the treatment may be carried out. in a tank and at room temperature for about five minutes; following which the'temperature oi. the solution is. then raised to about160 F., with steam, and held at that temperature for. about five minutes. The spent solution is then drained and the treated cloth rinsed and dried.

Where desired, it is possible to apply the condensation product by a padidng operation; for example, where the textile fabric receive not only a dye-fixing operation, but also other treatments which render them crush-resistant, shrink-proof or merely gives them an appearance and feel pleasing to the trade. These finishes are usually applied by padding, and it is possible to combine the dyefixing treatment with an otherwise subsequent treatment and apply them both in one padding operation. To do so, first prepare a two per cent solution of the condensation product in water: that is, two gallons of the condensation product and 98 gallons of water. The fabric is then passed through this solution, and then through squeeze rolls which remove most of the solution, leaving sixty per cent based on the weight of the dry fabric. In other words, 100 pounds of fabric is impregnated with 60 pounds of solution. The cloth is then dried on tenter frames.

The scope of my invention is defined in the appended claims.

I claim:

1. A process of producing a condensation product suitable for fixing substantive dyes on textiles, comprising reacting dicyandiamide with a copper salt selected from the group consisting of copper chloride and copper nitrate, to effect hydrolysis of said dicyandiamide and the combining thereof with the copper to produce a copper complex, and then reacting the copper complex with formaldehyde in solution of an acid selected from the group consisting of hydrochloric acid and nitric acid to produce a condensation product of iclcyandiamide, copper complex and formaldehyde.

2. A process of producing a condensation product suitable for fixing substantive dyes on textiles, comprising reacting dicyandiamide with an acid selected from the group consisting of hydrochloric acid and nitric acid to effect hydrolysis of said dicyandiamide into a form that will combine readily and permanently with a copper compound and formaldehyde, then reacting this hydrolyzed product with a copper salt selected from the group consisting of copper chloride and copper nitrate, in acid medium, and with forrmaldehyde, to produce a condensation product of dicyandiamide, copper complex and formaldehyde.

3. A process of producing a condensation product suitable for fixing substantive dyes on textiles, comprising reacting 1 mol of dicyandiamide with approximately 0.15 to 0. mol of copper chloride, to effect hydrolysis of said dicyandiamide and the combining thereof with the copper to produce a copper complex, and then reacting the copper complex with approximately 0.50 to 1.50 mols of hydrochloric acid and approximately 1.3 to 1.8 mol'sofformaldehr w produce. a. condensation product ofdicyandiamide, copper complex and formaldehyde.

4. A process of producing. a condensation product. suitable for fixing substantive dyes on textiles, comprising reacting 1 mol of dicyandiamide with. approximately 0.22. mol of copp r chloride to efiect an exothermic, reaction therebetween and the. hydrolysis of said dicyandiamide and the combining thereof. with the copper o produce a copper complex, and then condensing the copper complexwith approximately 1.5. mole of formaldehyde and. approximately 0.75 mol of; hydrochloric acid to produce a condensationproduct: of dicyandiamide, copper complex and. form.- aldehyde. 1

5. A process of producing a condensation product; suitablefor fixing substantivedyes ontextiles, comprising reacting 1, mol Of dicyandiamide with approximately 0A4 mol of. hydrochloric. acid to effect an exothermic reaction therebetween and the hydrolysis of said dicyandiamide, and then reacting this hydrolyzed product with approximately 0.22 mol of copper chloride and approximately 0.31 mol of hydrochloric acid, and approximately 1.5 mols of formaldehyde to produce a condensation product of dicyandiamide, copper complex and formaldehyde.

6. A process of producing a condensation prodnot suitable for fixing substantive dyes on textiles, comprising reacting 1 mol of dicyandiamide with approximately 0.44 mol of hydrochloric acid to effect hydrolysis of said dicyandiamide, next reacting this hydrolyzed product with approximately 1.5 mols of formaldehyde and approximately 0.31 mol of hydrochloric acid, and finally reacting this product with approximately 0.22 mol of copper chloride to produce a condensation product of dicyandiamide, copper complex and formaldehyde.

7. A process of producing a condensation product suitable for fixing substantive dyes on textiles, comprising heating an aqueous solution of dicyandiamide to approximately 170 F., adding copper chloride and allowing the exothermic reaction therebetween to take place for about seven to ten minutes and the temperature to rise to about 200 F., after which the temperature falls to about F., adding hydrochloric acid and formaldehyde solution and allowing the exothermic reaction therebetween to take place with a rise in temperature to approximately 200 F. and thereby produce a condensation product of dicyandiamide, copper complex and formaldehyde.

8. A process of producing a condensation product suitable for fixing substantive dyes on textiles, comprising heating an aqueous solution of dicyandiamide to approximately adding hydrochloric acid and allowing the exothermic reaction therebetween to take place for about seven to ten minutes and the temperature to rise about 200 F., then adding copper chloride, after which the temperature falls to about 140 F., adding hydrochloric acid and formaldehyde solution and allowing the exothermic reaction there between to take place with a rise in temperature to approximately 200 F. and thereby produce a condensation product of dicyandiamide, copper complex and formaldehyde.

9. A process of producing a condensation prod uct suitable for fixing substantive dyes on textiles, comprising heating an aqueous solution of dicyandiamide to approximately 170 adding hydrochloric acid and allowing the exothermic reaction therebetween to take place with a rise -in temperature to about 200 F afterawhich the temperature falls to about 140- F.,'adding additional hydrochloric acid andimmediately thereafter adding formaldehyde solution to reflect an exothermic-reaction at a'temperature of approximately 200 F., then adding copper chloride to produce a final condensation product of dicyandiamide, copper complex and formaldehyde.

10. A condensation product of dicyandiamide,

copper complex and formaldehyde resulting from the-process defined in claim 1.

11. A method of fixing substantive dyes on previously dyed textiles, comprising steeping said textiles with an aqueous'solution o'fa condensationjp'roduct of dicyandiamide,-copper complex and formaldehyde produced by the process definediniclaiml. v ,s

12; A method of fixing substantive dyes on previously dyed textiles, comprising steeping said textiles with an aqueous solution of a condensationwproduct of dicyandiamide, copper complex and formaldehydeliproduced by the process defined in claim 3. V V p SPANGLER.

REFERENCES CITED g vol. 43, p, 3620g, May 25, 1949.

Certificate of Correction Patent No. 2,576,241 November 27, 1951 MYRTLE J OANNE SPAN GLER It is hereby certified that error appears in the printed specification of the above numbered patent requiring correction as follows:

Column 1, line 19, for medinnf read medium; column 3, line 10, for these read there; line 12, for mold read moZ; column 4, line 2, for C1Cl .2H=O read 01601 21 1 0; line 19, for 180 read 18; column 5, line 18, for padidn read padding; line 19, for fabric" read fabrics; line 52, for idcyandiamide read dicyandiamz'de; lines 64 and 65, for forrmaldehydo read formaldehyde; and that the said Letters Patent should be read as corrected above, so that the same may conform to the record of the case in the Patent Olfioe.

Signed and sealed this 12th day of February, A. D. 1952.

THOMAS F. MURPHY,

Assistant Commissioner of Patents. 

1. A PROCESS OF PRODUCING A CONDENSATION PRODUCT SUITABLE FOR FIXING SUBSTANTIVE DYES ON TEXTILES, COMPRISING REACTING DICYANDIAMIDE WITH A COPPER SALT SELECTED FROM THE GROUP CONSISTING OF COPPER CHLORIDE AND COPPER NITRATE, TO EFFECT HYDROLYSIS OF SAID DICYANDIAMIDE AND THE COMBINING THEREOF WITH THE COPPER TO PRODUCE A COPPER COMPLEX, AND THEN REACTING THE COPPER COMPLEX WITH FORMALDEHYDE IN SOLUTION OF AN ACID SELCTED FROM THE GROUP CONSISTING OF HYDROCHLORIC ACID AND NITRIC ACID TO PRODUCE A CONDENSATION PRODUCT OF IDCYANDIAMIDE, COPPER COMPLEX AND FORMALDEHYDE. 